DE1447639A1 - Light-sensitive silver halide photographic emulsion - Google Patents

Description

DR Vg wolf / B ^ BTPi _S ^W np ^Ä RPAM ^T nPQ ^{25/22 7 STUTT} G ^A "ι 9 .. * .... Eär * ... 1964 QR ₁ -INO-WOlFr, BARTELS, DR. BRANDES long street 51

j REMOTE CALL: 294310 and 297295

'TELEPHONE: 0723312

Registration number. 119 24-4

Dr, Expl.

Eaatman Kodak Company, 343 State Street, Rochester, New York State, United States of America

Light-sensitive silver halide photographic emulsion

The invention relates to a photosensitive photographic silver halide emulsion containing a merocyanine and / or an undissociated cyanine dye which are derived from 3-thiätanon-l, l-dioxide. In particular, the invention relates to light-sensitive silver halide photographic emulsions containing an undissociated trinuclear Contain cyanine dye.

Polymethine dyes, such as, for example, merocyanine dyes are known. You can start from heterocyclic compounds from the ßhodanine series, Pyrazolone series, etc. can be produced.

The invention was based on the knowledge that starting out of derivatives of the four-membered heterocyclic * compound 3-thietanone-l, l-dioxide a new class of

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Dyes can be produced, which are, in very special excellent as an optical sensitization agent for phot ο graphic silver halide emulsions. The new cyanine dyes of the invention differ from the previously known cyanine dyes in that they do not contain the usual acid anion, such as an iodide or chloride ion, which is why they are classified as undissociated Dyes are referred to.

The photosensitive photograpiiische containing a Gyaninfarbstoff silver halide emulsion of the invention is therefore characterized in that it comprises a undissociated _s Cyariinfarbstoff of the following formulas

11

^Ig Η-ϊί (-CH = CH) -, - GC = GH-CH) _Ί = 0 _ν G ^ ²

pi "v y \ _R

or

II p

^ - Z 0 ₍ Z ₁ - ^ _n

RH (-aH = CH) ".-0 (= 0H-CH)", = C _V O (= CH-CH), _Ί = Ο- (ΟΗ = ΟΗ-), HE-,

ii "~ J- p - J_ ^^ jf CL - X III ™" J_ -L

has, where mean:
η and m positive numbers from 1 to 2j
ρ and ii numbers from 1 to 3 j

R and R-, alkyl groups of 1 to 12 carbon atoms; R ₂ and Ε., Hydrogen atoms, alkyl groups having 1 to 8 carbon atoms or mono-cyclic aryl groups, and

90.9812 / Ö831

BATH ORIGINAL

Z and Z ¹ visible metal atoms, which are required to complete a heterocyclic ring with 5 to 6 atoms.

R and E- can be, for example:

Methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, amyl, decyl, dodecyl, ß-hydroxyethyl, Y-hydroxypropyl, ßa-methoxyethyl, ß-ethoxyethyl, allyl, benzyl, ß-phenylethyl, ß-Carboxyethyl-, Oarboxymethyl-, Y-Carboxypropyl-, ß-acetoxyethyl, Ύ-acetoxypropyl, methoxycarbonylmethyl, Ethoxycarbonylethyl, sulfomethyl, ß-sulfoethyl, Y-sulfopropyl and CjT sulfobutyl groups, etc;

Rp and R can, apart from hydrogen, for example from the following Alkyl groups consist of:

Methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, amyl, hexyl and octyl groups. As monocyclic aryl groups z.ß. in question: phenyl, toly1 or ethylphenyl groups.

The heterocyclic rings formed with Z and Z ^ can z.j3. consist of thiazole rings, i.e. for example a thiazole, 4-methylthiazole, 5-methylthiazole, 4-phenylthiazole, 5-phenylthiazole, 4,5-dimethylthiazole, 4,5-diphenylthiazole or 4- (2-tliienyl) thiazole ring; Benzothiazole rings, like z.J. a benzothiazole, 4-chlorobenzothiazole, ^ -Uhlorobenzothiazol-, 6-Ohlorooenzothiazol-, 7-Ghlorobenzothiazol-, 4-methylbenzothiazole-, 5-methylbenzothiazole-,

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6-methyrbenzothiazole, 5-bromobensothiazole, 6-bromobenzothiazole, 4-phenylbenzothiazole, 5-phenylbenaothiazole, 4-methoxybenzothiazole, 5-metlioxybenzothiazole, 6-metiioxybenzothiazole, 6-iodobenzothiazole -, 4-ethoxybenzothiazole, 5-ethoxybenzothiazole, tetrahydrbenzothiazole, 5 _} 6-dimethoxybenzothiazole, 516-dioxymeth.ylenebenzothiazole, 5-hydroxybenzothiazole or 6-hydroxybenzothiazole, -, 5-methoxy-ß-naphthothiazole, 5-atlioxy-iB-naphtlioth.iazole, 7-methoxy-a-naphthothiazole or 8-methoxy-a-naphthothiazole ring \ Thianaplith.eno-7 '»β' _f 4» 5-thiazole rings, for example a 4 ^! -Methoxytliianaphtheno-7 ^l «6 *, 4»

5-thiazole rings, oxazole rings, such as a * B. a 4-methyloxazole, 5-methyloxazole, 4-piienyloxazole, 4.5 ^a * Mplisnyloxazole, 4-ethyloxasole ~ _{ 4 »5-dimetiiyloxazole or 5-hienyloxazole ring, benzoxazole, 5- Ohlorobenzoxazole, 5-pnenylbenzoxazole, 5-methylbenzoxazole, 6-methylbenzoxazole-, 5,6-methylbenzoxazole-, 4,6-methylbenzoxazole-, 5-methoxybenzoxazole-, 6-methoxybenzoxazole-, 5-ethoxybenzene, 5-methoxybenzoxazole- 6-ChlorobenEoxazole, 5-Hydroxybenzoxazole or 6-HydroxybenBOxazole ring \ Uaphthoxazole rings, such as an o-naphthoxazole or ß-naphthoxazole ring | Selenazole rings, such as, for example, a 4-methylselenazole or 4-plienylselenazole ring; benzobelenazole rings, such as, for example, a benzoselenazole, 5-chlorobenzoobelenazole, 5-methoxybenzoselenazole, 5-hydroxybenzoselenazole or tetrahydrobenzoselenazole ring; Naphthoselenazole rings such as a

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a-naphthoselenazole ring or ße naphthoselenazole ringj TMazoline rings, such as a thiazoline or 4-methylthiazoline ringj 2-ghinoline rings, such as quinoline, 3-methylquinoline, 5-methylquinoline, 7-methylquinoline, 8-methylquinoline, 6-olilorooliinolin-, 8-chloroquinoline-, 6-methoxyquinoline-, 6-Ätlioxychinolin-, 6-Hydroxychinolin- or 8-HydroxycliirLoline rings; 4-ohinoline rings, such as 3. Ohinoline, 6-methoxyquinoline, 7-methylquinoline or 8-Iletiiyloliinolinringen} 1-isoquinoline rings, such as z.ß, Isoquinoline or 3,4-dihydroisoohinoline rings; 3,3-dialkylindolenin rings, such as 3,3-Mmethylindolenin-, 313,5-Trimetiiylindolenin- or 3,3,7-trimethylindolenine rings; 2-pyridine rings, such as pyridine, 3-methylpyridine, 4-methylpyridine, 5-methylpyridine, 6-I, ietliylpyridine, 3,4-dimethylpyridine, 3,5-dimethylpyridine-, 3,6-dimethylpyridine-, 4,5-dimethylpyridine, 4-chloropyridine, 5-chloropyridine, 6-GJiloropyridin-, 3-Hydroxypyridin-, 4-Hydroxypyridin-, 5-hydroxypyridine, 6-hydroxypyridine, 3-phenylpyridine, 4-plienylpyridine or 6-plienylpyridine rings; 4-pyridine rings, such as 2-methylpyridine, 3-methylpyridine, 2-chloropyridine, 3-chloropyridine, 2,3-dimethylpyridine, 2,5-methylpyridine, 2-hydroxypyridine, or 3-hydroxypyridine rings.

As. particularly advantageous sensitizers for photographic silver halide emulsions have the new trinuclear dyes of the formula II, namely

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■ - 6 -

both the bis and the unsymmetrical series have been shown.

The dyes of the formula I added to the silver halide emulsions, in which ρ is a number such as 2 or 3, can are produced by reacting 3-thiethanone-1,1-dioxide the general formula:

Il

in

0 0

wherein Rp and R, have the meaning given, with a quaternary cyclammonium salt of the following general Formula:

^ - -Z- _N

ITo RI (= CH-CH) "-, = 0 (-CH = GH). - ¥ - R _K

x R ₄

where η, R and Z have the meaning given, j is an integer such as 1 or 2, R has the meaning of an acyl group, a monobasic carboxylic acid having 2 to 7 carbon atoms, such as an acetyl, propionyl, butyryl or 3enzoyl group; R ^ is a monocyclic aryl group having 6 to 7 carbon atoms, such as a phenyl or solyl group and where X is an acid anion, such as a chloride, bromide, iodide, thiocyanate, sulfamate, methyl sulfate, ethyl sulfate. Perchlorate ,. p- Toluenesulfonate ion or γ \ ρ.τρΊ. '

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The condensation can be carried out using approximately equimolecular Amounts of the compounds of formulas III and IV carried out at room temperature with efficient stirring reaction times of one hour or more Hours are applied and preferably working in an inert solvent, such as in methanol, ethanol, n-propanol, n-butanol, pyridine, Quinoline, isoquinoline, Ν, Ν-dimethylformamide, etc .. In more advantageous Way, the condensation is carried out in the presence of a basic condensing agent, such as in the presence of a trialky amine, e.g. triethylamine, Tri-n-propylamine, tri-n-butylamine, etc. or in the presence of H-methylpiperidine, H-ethylpiperidine, Η, Ν-dimethyl aniline and the like .. The dye formed can then be filtered off, for example washed with methanol and then recrystallized from ethanol.

The dyes represented by the formula I, in which p = 1 can easily be achieved by reacting 3-thiethanone-1,1-dioxide of formula III with a quaternary cycloammonium salt the following formula

V. R- N (= CH-OHL T = G-SRf-X

wherein n, X, R and Z have the meaning given and VGi'iii Rg is an alkyl group with 1 to 12 carbon atoms, a phenyl, benzyl or toly! group instead of the quater

909812 / 089Ί ^ ₀

-8 - ■■■■■■■■■■ .. "'-.- ■■

Nary salt of the formula IV is ₀ - ■

The processes for the preparation of the undissociated trinuelearic dyes preferably used according to formula II differ somewhat from one another, depending on the situation! , t Were you formula described except that - if dyes of the bis- or symmetric series or 4 unsymmetrical series are to be produced * The process for preparing the compounds trinuelearen is generally the same "as already described for the preparation of the compounds of the! a) as 3 ^ Thiätiianoii * -lil-dioxy4 4er formula XII such a compound is chosen "in which Rp" and R. represent hydrogen atoms that Ta) && ß ratio of the compounds of the formulas 112 and IV (oHet T) approximately one Mo! Ratio of one haul of the first-mentioned compound to two moles or meta?

For the preparation of compounds of the row j in dfiien d = 1, is a suitable method © is a connection ,, as shown by the formula I in which R ^ Rg'und hydrogen atoms darete3-l # n _r of approximately an equimolar amount of a quaternary Öycloammoniumsalzes, which can be represented by the following formula:

909812/0891.

VI. B ₁ - JT (= OH-OH-L T = G-SRi-. Ι 1 (m-1 ο

'■. Σ

In this formula, m, R-,, X and Z- have the meanings given, with the exception that Z- is a heterocyclic nucleus that differs from the nucleus Z and that Rg is an alkyl group having 1 to 12 carbon atoms, a benzyl -, phenyl or lolyl group.

To produce the series of compounds in which d = 2 or 3 - reference is made to the following examples 7 to 10 - a dye component of the formula I, in which R _? and R ~ represent hydrogen atoms, with an approximately equimolar amount of a quaternary cycloammonium salt, for example of the following general formula:

VII. R -, - NC = OH-OH) _n ,, = 0 (-OH = CH), - IT-Rp-

wherein m, j, R-,, R., R ^, X and Z-, have the meanings already given, with the exception that Z _{1 is} a heterocyclic ring different from Z, implemented.

The condensation reactions with the compounds of the formulas VI and VII can take place at temperatures up to reflux temperatures the reaction mixtures are carried out in the presence of a basic condensing agent

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and an inert solvent, as already mentioned in 'Connection with the establishment of the connections of the Formula I were mentioned. The trinuclear dye can be extracted from the reaction mixture by precipitation with a spruce solvent, e.g. isolated with methanol and water, whereupon it can be prepared from ethanol or FjN-dimethylformamide or mixtures the latter compound recrystallized with lower alkanols can be.

The heterocyclic compounds of the formulas IV, V, VI and VII are known and are described, for example, in /

the USA reissue patent 24 292 »

The 3-thiethanone-l, l-dioxides of the formula III can be prepared, for example, by hydrolysis of 3 »3- <dialkoxythiethane-1,1-dioxides obtained in the presence of dilute mineral acids ^ like. it for example in the ~ - -

is described »

In the preparation of the photographic emulsions the invention is expediently proceeded in such a way that the new dyes in the washed, finished silver halide emulsion incorporated and thoroughly uniform in this be distributed. Method of incorporating dyes in emulsions are known and relatively easy to carry out.

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The dyes can be added, for example, in the form of solutions with suitable solvents. As suitable For example, methanol, isopropanol, pyridine etc. alone or in mixtures with one another have been found. To the silver halide emulsions that can be sensitized with the new sensitizing dyes belong to all those made using hydrophilic colloids that are known to disperse of silver halides, such as emulsions made using naturally occurring substances, such as gelatin, albumin, agar-agar, gum arabic ,. Alginic acid, etc. «However, emulsions which are suitable for sensitization are those which are produced using hydrophilic synthetic plastics such as polyvinyl alcohol, polyvinylpyrrolidone, gelulose ethers, partially hydrolyzed gelulose acetates and the like have been.

The concentration of the new dyes in the emulsions can vary widely. Appropriate concentrations can for example be between about 5 and about 100 mg per liter of flowable emulsion. In each individual case Concentration to be used depends on the type of photosensitive Compound in the emulsion as well as from the pronounced effects. The determination of the for each individual case The most suitable concentration required prepares the i'-a ei unarm no difficulties whatsoever.

909812/089 1

The preparation of a gelatin-silver halide emulsion according to the invention can be seen, for example, as follows

One of the new dyes is dissolved in a suitable solvent, after which a certain volume of this solution with, for example, 5 to 100 mg of dye is slowly added to about 1,000 carbons of a gelatin-silver halide emulsion. In most cases, 10 to 20 mg of dye per liter are sufficient Emulsion _{t to} achieve maximum sensitization effects when using a conventional gelatine-silver bromide emulsion or gelatine-bromoiodide or gelatine-chlorobromite emulsion »When using fine-grain emulsions, which include most of the usual grelatine silver chloride emulsions, slightly higher dye concentrations are occasionally required to achieve optimal sensitization effects If an emulsion is used which contains another hydrophilic colloid instead of gelatin, the same applies. '_-''■ _ / ^;

The photographic emulsions of the invention can be applied to all conventional photographic support means, such as on paper, glass, cellulose nitrate Oelluloseacetat _t, synthetic fUmbildende Kunötstoffe, z »B. Polystyrene, polyester, polyamides, etc.

Of course, oils novel dyes can not be ^one introduced only from solutions in the emulsions but

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also in other ways. For example, it is possible to bring the dyes to use that a photographic plate or a photographic picture with Emulsions are immersed in the solution of a dye in a suitable solvent.

The silver halide photographic emulsions of the invention can, in addition to that already incorporated, sensitizing Dye also contain other additives, such as chemical sensitizers, such as sulfur containing sensitizers, e.g. allyl thiocarbamide, Thiourea, ally! Isothiocyanate, cystine and the like ,,, various Gold compounds, such as potassium chloroaurate, AuritriChlorid, etc., for example in the United States patents 2,540,065, 2,597,856 and 2,597,915 have been.

The emulsions of the invention can further contain a wide variety of palladium compounds, such as, for example Palladium chloride as described in U.S. Patent 2,540,086; potassium chloropalladate such as in U.S. Patent 2,598,079 or mixtures of various sensitizers. Also, the emulsions of the invention may contain antifoggants such as ammonium chloroplatinate such as described in U.S. Patent 2,566,245; Ammonium chloroplatinite, as described in US patent specification 2,566,263

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wrote; Benzotriazole, nitrobenzimidazole, 5-nitroindazole, Benzidine, mercaptans and derglo, such as from Mees in "The Theory of the Photographic Process", publisher Macmillan, 1942, page 460, or mixtures thereof. Furthermore, the emulsions can contain hardeners be added, such as formaldehyde, 'as in U.S. Patent 1,763,533, ghromaluminum sulfate as described in U.S. Patent 1,763,533, Glyoxal as described in U.S. Patent 1,870,354; Dibromoacrolein, such as in the British patent 406 750, etc. Color couplers can also be added to the emulsions, such as those used, for example in U.S. Patents 2,423,730 and 2,640,776, or mixtures thereof. After all, you can Emulsions are also incorporated into dispersants for color couplers, as described, for example, in the US patents 2 322 .027 and 2 304 940.

Some particularly advantageous dyes and processes for their preparation are described in the following examples. - -

Example 1. "■ ',..

2- / r3-ethyl-2-benzoxazolinylidene) ethylidene7-3-thietanone-1,1-dioxide

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-.15 -

H47639

= OH - OH =

! I

In 10 ml of methyl alcohol, 0.24 g of 3-thiethanol * l, ldioxide (1 mol), 0.86 g of 2-β-acetanilidovinyl-3-ethyrbenzoxazolium iodide (1 mol) and 1.0 ml of triethylamine (1 mol + 250 fo ) solved. Measurement reaction mixture was stirred vigorously at room temperature for 80 minutes. A precipitate separated out from the solution. The reaction mixture was kept cool overnight. The precipitated crude dye was then filtered off, washed with methyl alcohol and dried. After 2-iiialiger recrystallization from ethyl alcohol, 0.029 g (5 ^L ß>) of the purified dye with an ocliuelzpunkt of 230-231 ° 0 dec. obtain.

Example 2

2,4-i3is / r3-ethyl-2-benzoxazolinylidene) ethylidene7-3-thietanone-1,1-dioxide

Il

^ 0

0 9 812/0891

1.0 g of 3-thietanone-l, l-dioxide (1 mol), 8.2 g of 2-ß-acetanilidovinyl-3-ethylbenzoxaeolium iodide (1 mol + $ 15) and 5 ml of triethylamine (1 mol + 330 #) _v . ·. solved. The reaction mixture was refluxed for 5 minutes. After cooling, the reaction mixture was diluted with 500 ml of water and allowed to stand in the cold overnight. The crude dye was then filtered off and dried. Haoh recrystallization from ethyl alcohol were 0.45 g (12 fi) of the purified dye with a »melting point of 228 to 230 ⁰ G dec. obtain.

Example 3

2,4-bis / t3-ethyl-2-benaothiazolinylidene} ethylidene / ^r -3-thiätkanosi-1,1-dioxide

Il

In 20 ml of ethyl alcohol, 0.3 S 3 (1 mol), 2.5 S 2-ß-AcetaniXidovinyl-3-ethylben «otliiazolium-5odid (2 mol) and 1 al! Priethylamine (1 mol + 180 #) were gtlBst, The reaction mixture was refluxed for 13 minutes and then left to stand in the kettle overnight. The crude dye was then filtered off, washed with ethyl alcohol.

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wax and dry. After recrystallization twice from pyridine and methanol, 0.45 g (36 <fo) of the purified dye with a melting point of 246-247 ° 0 dec. obtain.

Example 4

2,4-Bis ^ 1,3 »3-trimethyl-2-indolinylidene) ethylidene7-3-thietanone-1,1-dioxide

GH

C = CH-GH = G

In 15 ml of ethyl alcohol, 0.24 g of 3-thietanone-l-dioxide was added (1 mole), 1.8 g of 2-ß-acetanilidovinyl-1,3,3-trimethylpseudoindolium iodide (2 mol) and 1 ml of triethylamine (1 mol + $ 250) dissolved. The reaction mix lasted 7 minutes heated under reflux and then left in the cold overnight calmly. The precipitated crude dye was then filtered off, washed with methyl alcohol and dried. To Recrystallization twice from pyridine and methanol gave 0.38 g (39 5 ^) of the purified dye with a melting point from 255 - 258 G dec. obtain.

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Example 5

2,4-bis / T'l-ethylnaphtho / ^< ~ 1,2-d7 * tiiiazolin-2-ylidene.) Ethylidene7 ^; 3-thietanone-l, l-dioxide

G = GH-OH = G

O = CH-GH = G

In 15 ml of ethyl alcohol, 0.24 g of 3-ethanone-l, l-dioxide (1 hol), 2.0 g of 2-ß-anilinovinyl-l-ethylnaphthol / l, 2-dfthiazolium-p-toluenesulfonate (2 moles ), 2 ml acetic anhy-. drid (1 mol + 4-00 f =) and 1 ml of triethylamine (1 mol + 250 fi) dissolved. The reaction mixture was refluxed for 18 minutes and then allowed to stand in the cold overnight. The precipitated crude dye was filtered off, washed with methyl alcohol and dried. The oil dye Y / was then introduced into 25 ml of boiling pyridine, whereupon it was allowed to cool and 25 ml of methyl alcohol were added to the reaction mixture. The residue is poured into 100 ml of boiling pyridine with stirring and then filtered off while hot. The residue was washed with methyl alcohol and then dried. Subject 2 recrystallization from dimethylformamide, 0.007 g (0.6 ^c / o) of the purified dye with a melting point of 254-256 ⁰ O dec. obtain.

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Example 6

2,4-bis / T3-methyl-2-thiazolidinylidene) ethylidene7-3-thietanone-1,1-dioxide

O ~

TC-OH-OH = O ^ ^ O = OH-OH = O " " ²

OH ₃ "

OH ₃

In 15 ml of ethyl alcohol, 0.24 g of 3-thietanone-1,1-dioxide (1 mol), 1.4 g of 2-ß-anilinovinyl-3-methylthiazolium3odide (.2MoI) ₁ 2 ml of acetic anhydride (1 mol + 400 f >) and 1 ml of triethylamine (1 mol + 250 fi) dissolved. The reaction mixture was then refluxed for 1 minute and allowed to stand in the cold overnight. The precipitated crude dye was then filtered off, washed with methyl alcohol and dried. After recrystallization from pyridine and methanol, 0.006 g (0.8 #) of the pure dye with a melting point of 243 to 245 ⁰ G dec. obtain"

Example 7

2- (3-Ethyl-2-benzothiazolinylidene) -4- / T3-ethyl-2-benzoxazolinylidene) ethylidene7-3-thietanone-1,1-dioxide

O "= OH-GH = O

9 09812/0891

In 30 ml of dimethylformamide, 0.58 g of 2- / r3-ethyl-2- "benzoxazolinylidene) ethylidene7-3-thietanone-l, l-dioxide _> were prepared as described in Example 1", <1 MqI), 1, 00 g of 3-ethyl-2-phenylthiobenzothiazoliiini3odid (1 mol + 25 °) and 2 ml of triethylamine (1 mol + $ 600) dissolved * The reaction mixture was refluxed for 2 minutes, 'After cooling, the reaction mixture was washed with methanol and Yfasser diluted 'Then the crude! Dye was filtered off, with. Water washed and dried «, After 2 recrystallization from dimethylformamide and methanol, 0 _f 03 S (3 ^) of the purified paraffin with a melting point of 257 to 258 ⁰ G dec. obtain.

Example 8

2-benzozaEolinyliden) äthylidenJ-J-thietanone-1,1-dioxyä

In 28 ml of dimethylformamide were 2 - / ^ 3-ethyl-2-benzoxazolinylidene) _{äthyliden2-5-thiätanon-l?} (| L-dioxide (1 mole), prepared as _p described in Example 1 0 90 g of 2-ß-acetanilidovinyl -3-äthylbenzothiazolium3odid (1 mol) and 2 ml of triethylamine (1 mol + 600 #) 'dissolved

S098 12/089 '!

was refluxed for 3 minutes. After cooling \, the mixture was diluted with methanol and water "Then \, the crude precipitated dye was filtered off washed with water and dried _g After 2 recrystallizations from ethyl alcohol was added 0.36 g (37 f <>) of the dye having a melting point obtained from 230 to 232 ⁰ G dec.

3example 9

2- / r3-Ethyl-2-benzoxazolinylidene) ethylidene7-4- (l-methyl-2 (1H) -quinolylidene) -3-thietanone-l, l-dioxide

Il

In 11 ml of dimethylformamide, 0.44 g of 2- / C 3-Äthy1-2-benzoxaz'olinyliden) äthyliden7-thietanone-l, l-dioxide (1 mol), prepared as described in Example 1, 0.75 g of 1- Methyl-2-phenylthioquinolinium; iodide (1 mol + 33 ^B / °) and 1.5 ml of iriethylamine (1 mol + 600 fo) dissolved. The reaction mixture was refluxed for 4 minutes and then allowed to stand in the cold for 2 hours. By diluting the quenched reaction mixture with methanol and rubbing the container walls with a glass rod, the crude fell. dye

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which was then filtered off and dried. After recrystallization twice from dimethylformamide and methanol, 0.11 g ($ 17) of the dye with a melting point of 260 to 261 ⁰ O dec. obtain.

Example 10 '.

2- / T3-ethyl-2-benzoxazoline3Tlidene) ethylidene7-4- (l-methylnaphthol / 1,2-d7thiazolin-2-ylidene) -3-thietanone-l, l-dioxide

G = GH-GH = G

G =

In 11 ml of dimethylformamide, 0.29 g of 2- / T 3-ethyl-2-benzoxazolinylidene) ethylidene7-3-thietanone-1,1-dioxide (1 mol), prepared as described in Example 1, 0.50 g of 1- Methyl 2-methylthionaphtho / 1,2-d7thiazolium-p-toluenesulfonate (1 mol + 20. #) And 1 ml of triethylamine (1 mol + 600 y> dissolved The reaction mixture was refluxed for 5 minutes, cooled and then with methanol the precipitated diluted. crude dye was then filtered off and getrocknetο compartment 2 recrystallizations from dimethylformamide and methanol was added 0.09 g (18 ° sss) of the purified dye having a melting point 272-273 ⁰ dec g, obtained

90S812 / Ö891

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The sensitizing effect that can be achieved with the new dyes is shown in the table below. The dyes were used in a silver bromoiodide emulsion containing 0.77 mole percent iodide. The type of emulsion used is, for example, from Trivelli and Smith, in Phot. Journal, 79, 330 (1939). The dyes were brought into the emulsions in the form of solutions with suitable solvents. After digestion at 50 ⁰ O for 10 minutes, the. Emulsions on an oil

2 loose acetate film carriers layered. On an area of 929 cm

432 mg of silver were used. Samples of the films obtained were placed on a sensitometer, a step wedge spectrograph exposed ,. Developed, fixed, washed and dried in a developer for 3 minutes. The following results were obtained:

Awareness levels

dye Awareness raising Awareness from example repay (mu) maximum (mji) 2 up to 700 650 / '^ ⁵ 575 to 745 710 4th 565 to 695 670 S 5 615 to 800 775 χ. 6th up to 650 600

The games 2 through 6 describe preferred trinuclear ones Dyes.

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Claims (1)

Claim 1 "Photosensitive photographiache, a silver halide emulsion containing ßtjMOtimtarbetoff, characterized labeled in» is characterized in that it rbatoff a undieeosilerten fc of the following Formelnι J ₁ -OJI © the ES (-OH-OHJj ₁ J-Cf-OH-OH) _x «0 has, where mean »
η and m positive numbers τοη 1 to 2j
ρ and d numbers from 1 to 3 | R and R ^ alkyl groups with 1 to 12 carbon atoms; R ₂ and R * hydrogen atoms, alkyl groups with 1 to 8 carbon atoms or monocyclic aryl groups and % and Z ^ Kichtaetallatome, which are necessary to complete a heterocyclic ring with 5 to 6 atoms * 9098Ί 2 / U891 2. A photosensitive silver halide photographic emulsion according to claim 1, characterized in that it comprises a undissociated uyanine dye of the formula: GT! = GH-CH = C _V C S V = CH - GH = contains. 3 "Light-sensitive silver halide photographic emulsion according to claim 1, characterized in that it contains an undissociated gyanine dye of the formula: contain 4. Photosensitive silver halide photographic emulsion according to claim 1, characterized in that it contains an undissociated gyanine dye of the formula: »0 9812/0891 - 26 - ". , ^G Ti = CH = CH-C ^ 0 OH - OH = 0 contains. 5. A light-sensitive photographic silver halide emulsion according to claim 1, characterized in that it comprises a undissociated oyanine dye of the formula: Il O = OH-CH = O 'G = OH-OII = G' O ₂ H ₅ contains 6ο Light-sensitive photographic silver halidei'mlsion according to claim 1, characterized in that it contains an undissociated uyanine dye of the formula: contains, I! G = OH-OH = O O = GH-GH = O OH XXXXXXX 909812/0891 .27- HA7639 7. Photographic light-sensitive material consisting of of a support and a hydrophilic, photosensitive silver halide-containing colloid layer, characterized thereby draws that the hydrophilic layer is an undissociated dye of the following formulas: Il Z ^ _n / ° \ ^ Ep or RN (-CHeCH) _n-1 -C (-CH-CH) ₁ = CC (= CH-CH) ^ _1-1 = C- (CH = CH- has, where mean:
η and m are positive numbers from 1 to 2;
ρ and d are numbers from 1 to 3; R and R-, alkyl groups of 1 to 12 carbon atoms; Rp and R- hydrogen atoms, alkyl groups with 1 to 8 carbon atoms or monocyclic ^ aryl groups and Z and Z ₁ non-metal atoms, which are necessary to complete a heterocyclic ring with 5 to 6 atoms. 909812/0891